Reactive dyestuffs, their preparation and their use for dyeing materials containing OH or N

ABSTRACT

Dyestuffs of the formula ##STR1## wherein Fb, W, R 1 , R 2 , R 3 , n and m have the meaning given in the description, 
     and their use for dyeing and printing materials containing hydroxyl groups or nitrogen, such as textile fibres, filaments and fabrics of wool, silk or synthetic polyamide or polyurethane fibres, and for washfast dyeing and printing natural or regenerated cellulose. 
     The dyeings obtained are distinguished by good fastness to wet processing.

The invention relates to reactive dyestuffs of the formula ##STR2##wherein Fb denotes the radical of an organic dyestuff, W denotes adirect bond or a bridge member, W being bonded to a C atom of anaromatic-carbocyclic ring of the chromophor Fb,

R₁ denotes hydrogen, optionally substituted C₁ -C₄ -alkyl or aralkyl,

R₂ denotes substituted C₁ -C₄ -alkyl,

R₃ denotes hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, especiallychlorine, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkyl- or-dialkyl-aminocarbonyl, optionally substituted arylaminocarbonyl,sulpho, C₁ -C₄ -alkyl- or -dialkyl-aminosulphonyl, hydroxyl, optionallysubstituted C₁ -C₄ -alkyl- or aryl-carbonylamino, formylamino,oxalylamino, optionally substituted ureido or sulphomethylene,

n is 0, 1, 2 or 3 and

m is 1 or 2.

Fb preferably represents the radical of a watersoluble azo dyestuff,anthraquinone dyestuff, phthalocyanine dyestuff or formazan dyestuff,especially the radical of such a dyestuff which contains sulphonic acidgroups.

Examples of suitable bridge members W are: --SO--, --CO--,-alkylene--CO--, -arylene-, -arylene-SO₂ --, -arylene-CO--, -alkylene-or -amino-CO--, --SO₂ -arylene-, --SO₂ -alkylene, --SO₂ -alkarylene-,##STR3## wherein R₄ denotes hydrogen, optionally substituted C₁ -C₄-alkyl or aralkyl and

the alkylene, aralkylene and arylene groups can carry furthersubstituents.

Preferred dyestuffs within the scope of the formula I are those of theformula II ##STR4## wherein Fb, W, R₁, R₂, m and n have theabovementioned meaning.

Dyestuffs of the formula III ##STR5## wherein Fb, W, R₁, R₂, R₃ and mhave the abovementioned meaning,

are also of particular importance.

Examples of suitable substituents R₂ are C₁ -C₄ -alkyl substituted bysulpho, carboxyl, alkoxycarbonyl, cyano, halogen, alkoxy or, inparticular, hydroxyl, such as --CH₂ --SO₃ H, --CH₂ --COOH, --CH₂ --CH₂--CN, --CH₂ --CH₂ --Cl, --CH₂ --CH₂ --OCH₃, --CH₂ --CH₂ --OH, --CH₂--CH(OH)--CH₃ and --CH₂ --CH₂ --COOH.

Within the formulae (I), (II) and (III), Fb, described in the followingtext as the dyestuff

    Fb--H

without the reactive portion, preferably corresponds to the followingformulae:

1. Azo dyestuffs of the formula

    A--N═N--B                                              (IV)

wherein

A represents the radical of a heterocyclic or carbocyclic diazocomponent, preferably from the benzene, naphthalene or triazole series,and

B represents the radical of a heterocyclic, carbocyclic or CH-acidcoupling component, in particular the radical of an optionally furthersubstituted phenol, naphthol, aniline, naphthylamine, 5-aminopyrazole,5-pyrazolone, pyridone, aminopyridine, acetoacetic acid arylide, indoleor pyrimidine.

The substituents W are linked to the azo dyestuff via a C atom of thediazo component and/or of the coupling component.

Particularly valuable dyestuffs of this series are those which containwater-soluble groups, such as sulphonic acid groups or carboxyl groups.The azo dyestuffs can be metal-free or in the form of metal complexes,copper complexes, chromium complexes and cobalt complexes beingpreferred.

The groups which form metal complexes, preferably hydroxyl groups,carboxyl groups and amino groups, are in the ortho-position relative tothe azo group.

The diazo components A and the coupling components B can be substituted,for example by the following substituents: sulpho, nitro, halogen, suchas fluorine, chlorine and bromine, C₁ -C₄ -alkyl which is optionallysubstituted by chlorine, C₁ -C₄ -alkoxy, hydroxyl or cyano, C₁ -C₄-alkoxy which is optionally substituted by C₁ -C₄ -alkoxy, hydroxyl orcyano, C₁ -C₄ -alkylmercapto, C₁ -C₄ -alkylsulphonyl, phenyl or naphthylwhich is optionally substituted by sulpho, amino, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, nitro or halogen, trifluoromethyl, amino, hydroxyl, C₁ -C₄-alkylcarbonylamino, C₁ -C₄ -alkylsulphonylamino, benzoylamino orbenzenesulphonylamino which is optionally substituted by sulpho, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, nitro or halogen, phenyl-C₁ -C₄ -alkyl which isoptionally substituted in the phenyl nucleus by sulpho, C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, nitro or halogen, phenylazo or naphthylazo which isoptionally substituted in the phenyl nucleus or naphthalene nucleus byhydroxyl, amino, sulpho, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, nitro orhalogen, C₁ -C₄ -alkyl-carbonyloxy, benzoyloxy which is optionallysubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, nitro or halogen,amino-carbonyl, mono- or di-C₁ -C₄ -alkylamino, ureido, carboxyl, cyano,carboxamide or sulphonamide which is optionally substituted on thenitrogen by C₁ -C₄ -alkyl, phenyl or benzyl, it being possible for alkylto be further substituted by sulpho or sulphato and for phenyl andbenzyl to be further substituted by sulpho, C₁ -C₄ -alkyl, C₁ - C₄-alkoxy, halogen or nitro, C₁ -C₄ -alkylsulphonylaminosulphonyl orphenylsulphonylaminosulphonyl which is optionally substituted in thephenyl nucleus by methyl, methoxy, chlorine or nitro.

Preferred azo dyestuffs Fb-H correspond to the formula ##STR6## whereinA₁ denotes a phenyl or naphthyl radical which can be substituted bysulpho, carboxyl, nitro, chlorine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenylor naphthyl which is optionally substituted by sulpho, amino or C₁ -C₄-alkyl, amino, acetylamino, benzyl which is optionally substituted byamino, sulpho or C₁ -C₄ -alkyl, phenylazo or naphthylazo which isoptionally substituted by amino, C₁ -C₄ -alkyl, sulpho, C₁ -C₄ -alkoxyor hydroxyl or trifluoromethyl,

Z denotes hydroxyl, alkoxy which is optionally substituted by hydroxylor C₁ -C₄ -alkoxy or amino which is optionally substituted by C₁ -C₄-alkyl, phenyl or benzyl, it being possible for alkyl to be furthersubstituted by cyano, hydroxyl or C₁ -C₄ -alkoxy and for phenyl andbenzyl to be further substituted by methyl, methoxy, chlorine, nitro orsulpho, and

R₅, R₆ and R₇ independently of one another denote hydrogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, amino, C₁ -C₄ -alkylcarbonylamino, phenyl whichis optionally substituted by C₁ -C₄ -alkyl, amino, hydroxyl or sulpho.

Further preferred azo dyestuffs correspond to the formula ##STR7##wherein A₁, R₅, R₆, R₇ and Z have the abovementioned meaning.

Further preferred azo dyestuffs correspond to the formula ##STR8##wherein A₁ has the abovementioned meaning,

R₈ denotes amino or hydroxyl,

R₉ denotes C₁ -C₄ -alkyl, preferably methyl or carboxyl, and

R₁₀ denotes phenyl or naphthyl which is optionally substituted bychlorine, C₁ -C₄ -alkyl, sulpho, C₁ -C₄ -alkoxy or amino.

Another preferred group of azo compounds corresponds to the formula##STR9## wherein A₁ has the abovementioned meaning.

Dyestuffs of the formula ##STR10## wherein A₁, R₅, R₆ and R₇ have theabovementioned meaning,

are also particularly valuable.

Azo dyestuffs of the formula ##STR11## wherein R₁₁ denotes C₁ -C₄-alkyl, aryl, carboxyl or hydroxyl,

R₁₂ denotes cyano, carboxyl, sulpho, sulpho-C₁ -C₄ -alkyl oraminocarbonyl,

R₁₃ denotes hydrogen, C₁ -C₄ -alkyl, aryl or aralkyl and

A₁ has the abovementioned meaning,

and of the formula ##STR12## wherein R₁₂ and A₁ have the abovementionedmeaning,

R₁₄ denotes C₁ -C₄ -alkyl or amino and

R₁₅ denotes hydrogen or C₁ -C₄ -alkyl, are likewise preferred.

Preferred dyestuffs amongst those of the formulae (V) to (XI) are thosein which

A₁ represents the radical of an amine of the formula ##STR13## whereinR₁₆ denotes hydrogen, sulpho, hydroxyl, carboxyl or amino,

R₁₇ denotes hydrogen, chlorine, nitro, aminosulphonyl, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, amino, sulpho, hydroxyl or phenylazo or naphthylazo whichis optionally substituted in the phenyl or naphthyl nucleus by hydroxyl,sulpho or amino and

R₁₈ denotes hydrogen chlorine, nitro, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,or of the formula ##STR14## wherein R₁₆, R₁₇ and R₁₈ have theabovementioned meanings and

R₁₉ denotes hydrogen, chlorine, nitro, aminosulphonyl, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, amino, sulpho, hydroxyl or phenylazo or naphthylazo whichis optionally substituted in the phenyl or naphthyl nucleus by hydroxyl,sulpho or amino.

2. Anthraquinone dyestuffs of the formula ##STR15## wherein L denoteshydrogen or a substituent,

R₂₀ denotes hydrogen, alkyl or aralkyl and

p denotes an integer from 1 to 6,

the reactive radical being bonded to the amino group in the 4-positionvia the bridge member W.

Preferably, L represents hydrogen, halogen, in particular chlorine,amino or hydroxyl, or very particularly preferably sulpho, R₂₀represents hydrogen, C₁ -C₄ -alkyl or benzyl and p represents 1 or 2.

Examples of anthraquinone components which may be mentioned are:1-amino-4-(3'-amino-phenylamino)-anthraquinone-2,4'-disulphonic acid,1-amino-4-(4'-aminophenylamino)-anthraquinone-2,3'-disulphonic acid,1-amino-4-(4'-methyl-amino-phenylamino)-anthraquinone-2,3'-disulphonicacid, 1-amino-4-(4'-aminophenylamino)-anthraquinone-2,6-disulphonic acidand the corresponding -2,7-, -2,5- and -2,8-disulphonic acids,1-amino-4-(3'-aminophenylamino)-anthraquinone-2,5-, -2,6-, -2,7- or-2,8-disulphonic acid,1-amino-4-(3'-amino-phenylamino)-anthraquinone-2,4',5-trisulphonic acidand the corresponding -2,4',6-, -2,4',7- and -2,4',8-trisulphonic acids,1-amino-4-(4'-aminophenylamino)-anthraquinone-2,3',5-trisulphonic acidand the corresponding -2,3',8-trisulphonic acid,1-amino-4-(4'-aminophenylamino)-anthraquinone-2,2'-disulphonic acid,1-amino-4-(4'-methylamino-phenylamino)-anthraquinone-2,2'-disulphonicacid,1-amino-4-(5'-amino-2'-methyl-phenylamino)-anthraquinone-2,4'-disulphonicacid,1-amino-4'-(5'-amino-4'-methylphenylamino)-anthraquinone-2,2'-disulphonicacid,1-amino-4-(3'-amino-2'-methyl-phenylamino)-anthraquinone-2,5'-disulphonicacid, 1-amino-4-(5'-amino-2',6'-dimethylphenylamino)-anthraquinone-2,3'-and -2,4'-disulphonic acid,1-amino-4-(5'-amino-2',4',6'-trimethylphenylamino)-anthraquinone-2,3'-disulphonicacid,1-amino-4-(5'-aminomethyl-2',6'-dimethyl-phenylamino)-anthraquinone-2,3'-disulphonicacid,1-amino-4-(5'-methylaminomethyl-2',6'-dimethyl-phenylamino)-anthraquinone-2,3'-disulphonicacid,1-amino-4-(4'-methylaminomethyl-phenylamino)-anthraquinone-2,2'-disulphonicacid,1-amino-4-(4'-amino-3'-carboxy-phenylamino)-anthraquinone-2,6-disulphonicacid,1-amino-4-(5'-amino-2'-methoxy-phenylamino)-anthraquinone-2,4'-disulphonicacid, 1-amino-4-[4'-(4"-aminophenyl)-phenylamino]-anthraquinone-2,2",3'-trisulphonic acid,1-amino-4-(2',6'-dimethyl-3'-sulphonamido)-anthraquinone-2-sulphonicacid and 1-amino-4-(4'-amino-2'-carboxy-phenylamino)-anthraquinone-2,6-and -2,7-disulphonic acid.

3. Azaporphin dyestuffs of the formula

    Pc--SO.sub.2 --NH--R.sub.21 ].sub.q                        (XVI)

wherein

Pc denotes the radical of a copper phthalocyanine or nickelphthalocyanine which is optionally substituted by C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, sulpho or sulphonamide which is optionally monosubstituted ordisubstituted by C₁ -C₄ -alkyl, benzyl or phenyl,

R₂₁ denotes hydrogen, alkyl or aralkyl, preferably hydrogen, C₁ -C₄-alkyl or benzyl, and

q denotes a number from 1 to 4.

The reactive group is bonded to the nitrogen atom of the sulphonamidegroup via the bridge member W.

Those azaporphin dyestuffs in which Pc represents a copperphthalocyanine or nickel phthalocyanine radical which is optionallysubstituted by 1-3.5 sulphonic acid or sulphonamide groups arepreferred.

4. Formazan dyestuffs of the formula ##STR16## wherein M is a heavymetal atom, preferably a copper atom,

G₁ and G₂ are aromatic-carbocyclic or aromatic-heterocyclic rings whichcarry the substituents a and b in the o-position relative to theformazan nitrogen atoms,

a and b denote hydrogen, hydroxyl, carboxyl or aminosulphonyl,

W₁ denotes a direct bond or a bridge member and

R₂₂ denotes alkyl or aryl,

and the aromatic-carbocyclic or aromatic-heterocyclic rings G₁ and G₂can contain further substituents, such as C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,chlorine, bromine, amino or, preferably, sulpho.

Suitable aromatic-carbocyclic and aromatic-heterocyclic rings G₁ and G₂are preferably benzene rings and naphthalene rings.

Examples of suitable bridge members W₁ are --CONH--, --CO--or --SO₂ --.

Suitable alkyl R₂₂ is C₁ -C₄ -alkyl which is optionally substituted byC₁ -C₄ -alkoxy.

Suitable aryl R₂₂ is phenyl or naphthyl which is optionally substitutedby C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine, sulpho, amino orphenylazo, it being possible for the phenylazo groups to be furthersubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, nitro, chlorine, sulpho oramino.

Within the scope of the dyestuffs described above, those of the generalformula III in which R₂ is a 2-hydroxyethyl radical, in particular thoseof the formulae IV to XVII, are preferred.

Quite generally, those dyestuffs in which R₁ and R₃ denote H, R₂ denotes--C₂ H₄ OH and W denotes a direct bond and which contain 1-8 sulphonicacid groups are preferred.

The dyestuffs according to the invention are obtained by a process inwhich 2,4,6-trifluoro-1,3,5-triazine, dyestuffs or dyestuff precursorswhich contain at least one amino or amide group with at least onereactive hydrogen atom, and a compound ##STR17## are reacted in anydesired sequence.

Preferably, dyestuffs or dyestuff precursors containing amino or amidegroups are first reacted with 2,4,6-trifluoro-1,3,5-triazine and theproduct is then subjected to a condensation reaction with a compound##STR18##

Depending on the nature of the starting compounds used, this procedureis carried out in an organic, organic-aqueous or aqueous medium at lowtemperatures, preferably in the presence of alkaline condensing agents,such as pyridine or aqueous alkali metal carbonate, alkali metalbicarbonate or alkali metal hydroxide solutions.

In the case of dyestuff precursors, after the reaction with2,4,6-trichloro-1,3,5-triazine, the products are converted into thedesired dyestuffs in a suitable manner, for example by diazotising andcoupling.

The dyestuffs obtainable by the processes described above can besubjected to other reactions customary for dyestuffs. For example,metallisable dyestuffs can be treated with metal-donating agents, inparticular with chromium salts, cobalt salts, copper salts or nickelsalts, dyestuffs which contain reducible groups, in particular nitrogroups, can be reduced and dyestuffs which contain acylatable groups, inparticular acylatable amino groups, can be acylated.

Preferably, dyestuffs which contain amide or amino groups and have theformula ##STR19## wherein A, B, W and R₁ have the meaning given,##STR20## wherein L, R₂₀, W, R₁ and p have the meaning given, ##STR21##wherein Pc, R₂₁, W, R₁ and m have the meaning given, and ##STR22##wherein G₁, G₂, a, b, W₁, R₂₂, W and R₁ have the meaning given and

m denotes 1 or 2,

are reacted with 2,4,6-trifluoro-1,3,6-triazine and a compound ##STR23##by the process described above.

The new dyestuffs are valuable products which are suitable for the mostdiverse applications. Being water-soluble compounds, they are ofpreferred interest for dyeing and printing textile materials containinghydroxyl groups or nitrogen, in particular textile materials of naturaland regenerated cellulose, and furthermore of wool, silk or syntheticpolyamide or polyurethane fibres. They are distinguished by asurprisingly high degree of fixing.

The products are particularly suitable as reactive dyestuffs for dyeingcellulose materials by the techniques known for such dyeing.

For dyeing cellulose, the dyestuffs are preferably employed in anaqueous solution, to which alkaline substances, such as alkali metalhydroxides or alkali metal carbonates, or compounds which are convertedinto alkaline substances, such as alkali metal bicarbonates, can beadded. Other auxiliaries can be added to the solution, but these shouldnot react with the dyestuffs in an undesirable manner. Examples of suchadditives are surface-active substances, such as alkylsulphates,substances which prevent migration of the dyestuff, dyeing auxiliaries,such as urea (to improve the solubility and fixing of the dyestuffs), orinert thickeners, such as oil-in-water emulsions, tragacanth, starch,alginate or methylcellulose.

The solutions or pastes thus prepared are applied, for example bypadding in a padder (short liquor) or by printing, to the material to bedyed and the material is then heated to an elevated temperature,preferably 40° to 150° C., for some time. The heat treatment can becarried out in a hot flue, in a steamer, on heated rollers or byintroducing the material into heated concentrated salt baths; each ofthese treatments can be carried out by itself or the treatments can becarried out successively in any desired sequence.

If a padding liquor or dyeing liquor without an alkali is used, the drygoods are subsequently passed through an alkaline solution, to whichsodium chloride or sodium sulphate decahydrate is added. The addition ofsalt reduces migration of the dyestuff from the fibre.

The material to be dyed can also be pre-treated with one of theabovementioned acid-binding agents and then treated with a solution orpaste of the dyestuff, and finally, as indicated, the dyestuff is fixedat elevated temperature.

For dyeing from a long liquor, the meterial is introduced into anaqueous solution of the dyestuff (liquor ratio of 1:5 to 1:40) at roomtemperature and dyeing is carried out for 40 to 90 minutes, thetemperature being raised to 85° C. if appropriate and a salt, forexample sodium sulphate, and then an alkali, for example sodiumphosphates, sodium carbonate or alkalis, being added in portions. Thechemical reaction between the dyestuff and fibre occurs during thisprocedure. When the chemical fixing has taken place, the dyed materialis rinsed hot and then soaped, whereupon non-fixed residues of thedyestuff are removed. Dyeings which are outstandingly fast, especiallyto wet processing and light, are obtained.

In the so-called pad-cold batch process, subsequent heating of thepadded fabric can be spared by storing the fabric at room temperaturefor some time, for example 20 to 40 hours. A stronger alkali than in thedyeing process described above, from a long liquor, is employed in thisprocess.

For printing materials containing hydroxyl groups, a printing pasteconsisting of the dyestuff solution, a thickener, such as sodiumalginate, and an alkaline compound or a compound which splits off analkali on heating, such as sodium carbonate, sodium phosphate, potassiumcarbonate, potassium acetate or sodium bicarbonate or potassiumbicarbonate, is used and the printed material is rinsed and soaped.

If the dyestuffs contain groupings which form metal complexes, thefastness properties of the dyeings and prints can frequently be improvedby subsequent treatment of the material with agents which donate metals,such as copper salts, for example copper sulphate, or chromium salts,cobalt salts or nickel salts, such as chromium acetate, cobalt sulphateor nickel sulphate.

Textile materials containing amide groups, such as wool, silk orsynthetic polyamide or polyurethane fibres, are generally dyed in theacid to neutral range by the dyeing methods customary for thesematerials, it sometimes being advantageous finally to increase the pHvalue of the dyebath, for example to a pH of 6.5 to 8.5.

The dyestuffs are applied, for example, to the synthetic polyamidefabric in the form of solutions or, preferably, in a dispersed form andthe fabric is then after-treated, if appropriate together withacid-binding agents, such as sodium carbonate, preferably in relativelysmall amounts. Particularly favourable results are achieved with thosedyestuffs which are insoluble or only sparingly soluble in water. Thesedyestuffs are converted to a dyestuff dispersion by techniques which arein themselves customary, with the addition of the known auxiliaries, andare used as such in the dyebath and/or padding bath or in a printingpaste. The auxiliaries suitable for this use are, inter alia, compoundswhich prevent migration of the dyestuff on the fibre, such as celluloseethers, alkali metal chlorides and sulphates, wetting agents, such ascondensation products of ethylene oxide and fatty alcohols or phenols,sulphonated fatty alcohols, solvents, such as thiodiglycol, andfurthermore thickeners, such as starch, tragacanth, alginate thickener,gum arabic and the like.

The after-treatment of the dyeings, impregnations and prints obtained onthe polyamide fibre fabric is preferably carried out at a temperature of50°-110° C. over a period of 5 to 60 minutes. In this case also, if thedyestuffs used contain groupings which form metal complexes, thefastness properties of the dyeings can sometimes be improved by agentswhich denate metals, such as copper salts, for example copper sulphate,or chromium salts, cobalt salts or nickel salts, such as chromiumacetate, cobalt sulphate or nickel sulphate.

The dyeings obtainable with the new dyestuffs are generallydistinguished by good to very good fastness properties, in particular byoutstanding fastness to wet processing.

EXAMPLE 1

16 g of1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-4-(5"-amino-2"-sulphophenylazo)-5-pyrazoloneare dissolved in 300 ml of water. The pH value is adjusted to 4.0 andthe solution is cooled to 0°-5°.

3.0 ml of cyanuric fluoride are added dropwise to the solution in thecourse of 5 minutes. At the same time, the pH value is kept at 3.5-4.0by means of 20% strength sodium carbonate solution. The mixture issubsequently stirred for 15 minutes. 4.5 g of N-(2-hydroxyethyl)-anilineare then added to the solution and the pH value is rapidly adjusted to6.5. The mixture is kept at this value. Whilst subsequently stirring fortwo hours, the temperature is allowed to rise to 20°. The dyestuff,which has partly precipitated, is salted out completely with 30 g ofsodium chloride, filtered off, washed with 10% strength sodium chloridesolution and dried at 40° in vacuo. In the form of the free acid, thedyestuff corresponds to the formula ##STR24## and dyes cotton, from along liquor at 40°, in clear greenish-tinged yellow shades with goodfastness to light and wet processing.

If the 2,4-diaminobenzenesulphonic acid and the1-(2',5'-dichloro-4'-sulphophenyl)-methyl-5-pyrazolone in Example 1 arereplaced by the diazo components and coupling components indicated inthe table, further valuable dyestuffs which give the colour shadesindicated are obtained.

    __________________________________________________________________________    Ex-                                                                           ample                                   Colour shade                          No. Diazo component Coupling component  on cotton                             __________________________________________________________________________    2   2,4-diaminobenzenesulphonic                                                                   5-amino-3-methyl-1-(2'-methyl-4'-                                                                 yellow                                    acid            sulphonylphenyl)-pyrazole                                 3   2,4-diaminobenzenesulphonic                                                                   5-amino-3-phenyl-1-(2'-methoxy-5'-                                                                yellow                                    acid            sulphophenyl)-pyrazole                                    4   2,5-diaminobenzenesulphonic                                                                   5-amino-3-phenyl-1-(2'-methoxy-5'-                                                                yellow                                    acid            sulphophenyl)-pyrazole                                    5   2,4-diaminobenzenesulphonic                                                                   1-(β-carboxyethyl)-5-pyrazolone-                                                             greenish-tinged                           acid            3-carboxylic acid   yellow                                6   2,4-diaminobenzenesulphonic                                                                   1-(β-cyanoethyl)-5-pyrazolone-3-                                                             greenish-tinged                           acid            carboxylic acid     yellow                                7   2,4-diaminobenzenesulphonic                                                                   6-hydroxy-1,4-dimethyl-3-sulpho-                                                                  greenish-tinged                           acid            methyl-2-pyridone   yellow                                8   2,4-diaminobenzenesulphonic                                                                   4,6-dihydroxy-1-methyl-3-(N-                                                                      yellow                                    acid            methylaminocarbonyl)-2-pyridone                           9   2,4-diaminobenzenesulphonic                                                                   1-naphthol-4,7-disulphonic acid                                                                   orange-red                                acid                                                                      10  2,5-diaminobenzenesulphonic                                                                   2,4-diamino-5-cyano-6-(3'-sulpho-                                                                 yellow                                    acid            phenyl)-pyridine                                          11  2,4-diamino-5-chlorobenzene-                                                                  (4-amino-3,5-disulphophenyl)-                                                                     greenish-tinged                           sulphonic acid  acetoacetanilide    yellow                                12  2,4-diaminobenzenesulphonic                                                                   6-ureido-1-naphthol-3-sulphonic                                                                   orange                                    acid            acid                                                      13  2,4-diaminobenzenesulphonic                                                                   7-(4'-sulphophenylamino)-1-                                                                       brown                                     acid                                                                      14  2,4-diaminobenzenesulphonic                                                                   8-acetylamino-1-naphthol-3,6-                                                                     red                                       acid            disulphonic acid                                          15  2,5-diaminobenzenesulphonic                                                                   1-(4'-sulphophenyl)-3-carboxy-                                                                    reddish-tinged                            acid            5-pyrazolone        yellow                                16  2,5-diaminobenzenesulphonic                                                                   barbituric acid     greenish-tinged                           acid                                yellow                                17  2,5-diaminobenzenesulphonic                                                                   7-phenylamino-1-naphthol-3,6-                                                                     brown                                     acid            disulphonic acid                                          18  2,4-diamino-5-methoxybenzene-                                                                 7-phenylamino-1-naphthol-3,6-                                                                     brown-red                                 sulphonic acid  disulphonic acid                                          19  2,5-diaminobenzenesulphonic                                                                   7-amino-1-naphthol-3-sulphonic                                                                    red                                       acid            acid (coupled under acid conditions)                      20  2,5-aminobenzenesulphonic                                                                     7-methylamino-1-naphthol-3-sulphonic                                                              red                                       acid            acid (coupled under acid conditions)                      21  2,5-diaminobenzenesulphonic                                                                   7-amino-1-naphthol-4-sulphonic                                                                    red-violet                                acid            acid (coupled under acid conditions)                      22  2,5-diaminobenzenesulphonic                                                                   5-(2'-sulphophenylazo)-6-phenyl-                                                                  red                                       acid            amino-1-naphthol-3-sulphonic acid                         __________________________________________________________________________

EXAMPLE 23

16.0 g of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid aredissolved in 200 ml of water by adjusting the pH value to 5.5 with 20%strength sodium carbonate solution. The solution is cooled to 0°-5° and4.6 ml of cyanuric fluoride are then added dropwise in the course of 5minutes. The pH value is kept at 4.0-4.5 with 20% strength sodiumcarbonate solution during the dropwise addition, and the mixture is thensubsequently stirred at pH 4.5 for a further 10 minutes. 7.1 g ofN-(2-hydroxyethyl)-aniline are now added to the solution and the pHvalue is kept at 6.5-7.0. After subsequently stirring the mixture for2-3 hours, the condensation reaction has ended.

8.7 g of 2-aminobenzenesulphonic acid are dissolved in 100 ml of waterwhilst neutralising. The solution is cooled to 0°-5°, 10 ml ofconcentrated hydrochloric acid are added and diazotisation is carriedout by adding 25 ml of 2 N sodium nitrite solution dropwise. Aftersubsequently stirring the mixture for half an hour, any excess nitriteis removed with amidosulphonic acid.

The diazo compound is now added to the solution, prepared above, of thereactive coupling component at 0°-5° and the pH value of the couplingmixture is kept at 7.0-7.5 with 20% strength sodium carbonate solution.The mixture is subsequently stirred for 1 hour and the temperature isthen allowed to rise to 20°. The pH value is adjusted to 6.5 and thedyestuff is salted out of the solution with 150 g of sodium chloride,filtered off, washed with 25% strength sodium chloride solution anddried at 40° in vacuo.

The dyestuff, which, in the form of the free acid, corresponds to theformula ##STR25## dyes cotton, from a long liquor, in bluish-tinged redshades with good fastness properties.

EXAMPLE 24

28.5 g of the disodium salt of6-amino-1-hydroxy-2-(2'-sulphophenylazo)-naphthalene-3-sulphonic acidare dissolved in 900 ml of water. 6.0 ml of cyanuric fluoride are addeddropwise to the solution, cooled to 0°-5°, in the course of 15 minutesand the pH value is kept at 5.0-5.5 with 20% strength sodium carbonatesolution. The mixture is subsequently stirred for 15 minutes and 9.3 gof N-(2-hydroxyethyl)-aniline are then added dropwise. The pH value isthen kept within the limits of 6.5 and 7.0. The mixture is thensubsequently stirred for two hours, during which the temperature isallowed to rise to 20° and the above pH value is maintained further. Thedyestuff is then salted out with 180 g of sodium chloride, filtered offand washed with 10% strength sodium chloride solution. It issubsequently dried at 40° in vacuo.

The product, which, in the form of the free acid, has the formula##STR26## dyes cotton, from a long liquor, in yellowish-tinged orangeshades with good fastness to light and wet processing.

Comparable dyestuffs are obtained when 2-aminobenzenesulphonic acid and6-amino-1-naphthol-3-sulphonic acid are replaced by the diazo componentsand coupling components indicated in the following table.

    __________________________________________________________________________    Ex-                                                                           ample                              Colour shade                               No. Diazo component  Coupling component                                                                          on cotton                                  __________________________________________________________________________    25  4-aminobenzene-1,3-disulphonic                                                                 3-methyl-1-[6-amino-4,8-                                                                    yellow                                         acid             disulphonaphth-2-yl]-5-                                                       pyrazolone                                               26  2-aminonaphthalene-4,8-                                                                        3-methylaniline                                                                             yellow                                         disulphonic acid                                                          27  2-aminonaphthalene-4,6,8-                                                                      3-methylaniline                                                                             yellow                                         trisulphonic acid                                                         28  2-aminonaphthalene-6,8-                                                                        3-aminoacetanilide                                                                          yellow                                         disulphonic acid                                                          29  2-aminonaphthalene-3,6,8-                                                                      3-aminoacetanilide                                                                          yellow                                         trisulphonic acid                                                         30  4-aminobenzene-1,3-disulphonic                                                                 3-aminophenylurea                                                                           yellow                                         acid                                                                      31  2-aminobenzene-1,4-disulphonic                                                                 3-aminophenylurea                                                                           yellow                                         acid                                                                      32  1-amino-4-(2',5'-disulpho-                                                                     3-aminophenylurea                                                                           reddish-tinged                                 phenylazo)-naphthalene-6-      brown                                          sulphonic acid                                                            33  2-aminonaphthalene-3,6,8-                                                                      3-aminophenylurea                                                                           yellow                                         trisulphonic acid                                                         34  2-amino-5-(4'-sulphophenyl-                                                                    6-amino-1-naphthol-3-                                                                       bluish-tinged                                  azo)-benzenesulphonic acid                                                                     sulphonic acid                                                                              red                                        35  2-amino-1-sulphomethyl-.                                                                       6-amino-1-naphthol-3-                                                                       red                                            naphthalene-5-sulphonic acid                                                                   sulphonic acid                                           36  2-amino-5-methoxy-benzene-                                                                     6-amino-1-naphthol-3-                                                                       scarlet                                        sulphonic acid   sulphonic acid                                           37  2-aminonaphthalene-1,5-                                                                        6-amino-1-naphthol-3-                                                                       orange                                         disulphonic acid sulphonic acid                                           38  2-aminonaphthalene-3,6-                                                                        6-amino-1-naphthol-3-                                                                       orange                                         disulphonic acid sulphonic acid                                           39  2-amino-5-(4'-sulphophenyl-                                                                    1-aminonaphthalene-6-                                                                       yellow-brown                                   azo)-benzenesulphonic acid                                                                     sulphonic acid                                           40  1-amino-4-(2',5'-disulpho-                                                                     1-aminonaphthalene-7-                                                                       red-brown                                      phenylazo)-naphthalene-6-                                                                      sulphonic acid                                               sulphonic acid                                                            41  2,5-dimethoxy-4-(2,5-disulpho-                                                                 3-ethylaminophenylurea                                                                      brown                                          phenylazo)-aniline                                                        42  1-amino-4-[4',8'-disulpho-                                                                     1-aminonaphthalene-6,8-                                                                     brown                                          naphthyl-2-azo]-naphthalene-                                                                   disulphonic acid                                             7-sulphonic acid                                                          43  1-amino-4-[  4',8'-disulpho-                                                                   1-aminonaphthalene-8-                                                                       brown-red                                      naphthyl-2-azo]-naphthalene-                                                                   sulphonic acid                                               6-sulphonic acid                                                          44  aniline          8-amino-1-naphthol-3,6-                                                                     bluish-tinged                                                   disulphonic acid                                                                            red                                        45  2-amino-5-methylbenzene-                                                                       8-amino-1-naphthol-3,6-                                                                     red                                            sulphonic acid   disulphonic acid                                         46  2-aminonaphthalene-1-                                                                          8-amino-1-naphthol-3,6-                                                                     claret red                                     sulphonic acid   disulphonic acid                                         47  2-aminonaphthalene-1,5-                                                                        8-amino-1-naphthal-3,6-                                                                     red                                            disulphonic acid disulphonic acid                                         48  2-aminonaphthalene-1,5-                                                                        8-amino-1-naphthol-3,5-                                                                     red                                            disulphonic acid disulphonic acid                                         49  2-amino-1-sulphomethyl-                                                                        8-amino-1-naphthol-3,5-                                                                     ruby                                           naphthalene-5-sulphonic                                                                        disulphonic acid                                             acid                                                                      50  2-methoxy-4-(2'-sulpho-                                                                        8-amino-1-naphthol-3,6-                                                                     blue                                           phenylazo)-5-methylaniline                                                                     disulphonic acid                                         51  1-amino-4-[4',6',8'-tri-                                                                       3-methylaniline                                                                             brown                                          sulphonaphthyl-2-azo]-                                                        naphthalene-6-sulphonic acid                                              __________________________________________________________________________

EXAMPLE 52

137.7 g of the copper complex azo dyestuff which is obtained from thediazonium salt of 2-amino-5-sulphobenzenecarboxylic acid by couplingwith 3-methyl-1-[6'-amino-4',8'-disulphonaphth-2-yl]-5-pyrazolone andcoppering the product in an acetate-buffered solution with copper-IIsulphate solution are dissolved, at pH 5, in 3.5 l of water and thesolution is cooled to 0°. 20 ml of cyanuric fluoride are added in thecourse of 15 minutes, the pH and temperature are kept constant and themixture is then subsequently stirred for a further 15 minutes. 31 g ofN-(2-hydroxyethyl)-aniline are now added, the pH value is kept at6.5-7.0 and the temperature is allowed to rise to about 20° C. Aftersubsequently stirring the mixture for 2-3 hours, the condensationreaction has ended. The dyestuff is salted out at room temperature,filtered off and dried.

The dyestuff, which, in the form of the free acid, corresponds to theformula ##STR27## dyes cotton and viscose staple in a yellow which isvery fast to light and wash-resistant.

EXAMPLE 53

18.9 g of 2-aminophenol-4-sulphonic acid are diazotised and thediazotisation product is coupled to 31.9 g of8-amino-1-naphthol-3,5-disulphonic acid at pH 8. After the couplingreaction, the mixture is warmed to 90° C. with 16 g of copper sulphateat pH 5 for 1 hour. The copper complex dyestuff is salted out andfiltered off. The moist paste is dissolved in 600 ml of water andcondensation reactions are carried out, first with 10 ml of cyanuricfluoride at pH 4.0-4.5 and at 0° C. and then with 15.5 g ofN-(2-hydroxyethyl)-aniline at pH 7 and at room temperature, in each casewith the aid of 20% strength sodium carbonate solution. The dyestuff issalted out, filtered off and dried in vacuo.

Cellulose fibres are dyed blue-violet by this dyestuff.

In the form of the free acid, the dyestuff corresponds to the formula:##STR28##

Further copper complex reactive dyestuffs are obtained when the diazocomponents and coupling components listed in the following table areused instead of the 2-aminophenyl-4-sulphonic acid and8-amino-1-naphthol-3,5-disulphonic acid.

    __________________________________________________________________________    Ex-                                                                           ample                                    Colour shade                         No. Diazo component  Coupling component  on cotton                            __________________________________________________________________________    54  2-amino-5-sulphobenzoic acid                                                                   6-amino-1-naphthol-3-sulphonic acid                                                               brown-red                            55  1-amino-2-naphthol-4-                                                                          6-amino-1-naphthol-4,8-disulphonic                                                                navy blue                                sulphonic acid   acid                                                     56  2-aminonaphthalene-4,8-di-                                                                     8-amino-1-naphthol-3,6-disulphonic                                                                reddish-tinged                           sulphonic acid (oxidatively                                                                    acid                blue                                     coppered)                                                                 57  2-aminonaphthalene-6,8-di-                                                                     6-amino-1-naphthol-4,8-disulphonic                                                                navy blue                                sulphonic acid (oxidatively                                                                    acid                                                         coppered)                                                                 58  2-amino-6-nitronaphthalene-                                                                    6-amino-1-naphthol-3-sulphonic acid                                                               blue                                     4,8-disulphonic acid                                                          (oxidatively coppered)                                                    59  2,4-diaminophenol                                                                              8-amino-1-naphthol-5,7-disulphonic                                                                bluish-tinged                                             acid                violet                               60  6-nitro-1-diazo-2-naphthol-                                                                    8-amino-1-naphthol-5,7-disulphonic                                                                blue                                     4-sulphonic acid (reduced)                                                                     acid                                                     61  2,4-diaminophenyl-6-sulphonic                                                                  8-amino-1-naphthol-5,7-disulphonic                                                                blue                                     acid             acid                                                     62  4-(2-sulphophenylazo)-2-                                                                       6-amino-1-naphthol-3,5-disulphonic                                                                blue                                     methoxy-5-methylaniline                                                                        acid                                                     63  2,5-diaminobenzenesulphonic                                                                    4-(2'-hydroxy-5-sulphophenylazo)-                                                                 brown                                    acid             resorcinol                                               __________________________________________________________________________

EXAMPLE 64

109 g of the copper complex dyestuff obtained from the diazonium salt of8-amino-1-phenyl-sulphonyloxynaphthalene-3,6-disulphonic acid bycoupling to 6-acetylamino-1-naphthol-4,8-disulphonic acid at pH 8,subjecting the coupling product to oxidative coppering with coppersulphate and hydrogen peroxide and hydrolysing the N-acetyl andO-phenylsulphonyl groups are dissolved, at pH 5.5-6.0, in 4 l of waterand successive condensation reactions are carried out with 14 ml ofcyanuric fluoride at pH 6 and at 0° C. and with 21.7 g ofN-(2-hydroxyethyl)-aniline at pH 7 and at room temperature. The dyestuffcorresponds, in the form of the free acid, to the formula: ##STR29## anddyes cotton and viscose staple blue.

EXAMPLE 65

If the 8-amino-1-phenylsulphonyloxynaphthalene-3,6-disulphonic acid inExample 64 is replaced by an equivalent amount of8-amino-1-phenylsulphonyloxynaphthalene-3,5-disulphonic acid, a dyestuffwhich dyes cotton and viscose staple in very fast greenish-tinged blueshades is obtained.

EXAMPLE 66

18.9 g of diazotised 2-aminophenol-4-sulphonic acid are coupled to 64.7g of the copper complex azo dyestuff obtained from the diazonium salt of6-amino-1-naphthol-4,8-disulphonic acid by coupling to6-amino-1-naphthol-3-sulphonic acid and subsequently subjecting thecoupling product to oxidative coppering. After salting out and filteringoff the dyestuff, the moist dyestuff paste is dissolved in 1.8 l ofwater and the dyestuff is coppered a second time with 25 g of coppersulphate at pH 5 and at 50° C. in the course of one hour and is isolatedagain. The dyestuff paste is stirred in 1.9 l of water and condensationreactions are carried out, first with 10 ml of cyanuric fluoride at pH 5and at 0° C. and then with 15.5 g of N-(2-hydroxyethyl)-aniline at pH 7and at room temperature.

The dyestuff, which, in the form of the free acid, corresponds to theformula: ##STR30## dyes cotton and viscose staple blue.

EXAMPLE 67

47.4 g of the 1:1 complex obtained by coupling the diazonium salt of2-amino-4,6-dinitrophenyl to 2-aminonaphthalene-6-sulphonic acid andthen cobalting the coupling product with cobalt sulphate heptahydrate atpH 5 and at room temperature are reacted, in 1,250 ml of water at pH 11and at 45° C., with 55.4 g of the azo dyestuff obtained by coupling thediazonium salt of 2-amino-4-nitrophenyl-6-sulphonic acid to6-amino-1-naphthol-3-sulphonic acid to give the 1:2 cobalt complex. Thisreaction takes about 2.5 hours. The dyestuff is then salted out withsodium chloride and filtered off.

The paste is suspended in 1.5 l of water and condensation reactions arecarried out, first with 10 ml of cyanuric fluoride at pH 5 and at 0° C.and then with 15.5 g of N-(2-hydroxyethyl)-aniline at pH 7 and at roomtemperature.

Thereafter, the dyestuff is salted out, filtered off and dried in vacuo.The unsymmetric 1:2 cobalt complex thus prepared dyes cotton and viscosestaple in dark brown shades. In the form of the free acid, itcorresponds to the formula: ##STR31##

Symmetric 1:2 cobalt complex azo dyestuffs are obtained when the diazocomponents and coupling components mentioned in the following table areused.

    __________________________________________________________________________    Ex-                                                                           ample                             Colour shade                                No. Diazo component                                                                              Coupling component                                                                           on cotton                                   __________________________________________________________________________    68  2-aminophenol-4-sulphonic acid                                                               acetoacetic acid 4-aminoanilide                                                              yellow                                      69  2-amino-4-nitrophenol-6-                                                                     4-aminophenol  brown                                           sulphonic acid                                                            70  2-amino-4-nitrophenol-6-                                                                     3-amino-2-naphthol-5,7-                                                                      reddish-tinged                                  sulphonic acid disulphonic acid                                                                             brown                                       71  2-amino-4-nitrophenol                                                                        8-amino-1-naphthol-3,6-                                                                      grey                                                           disulphonic acid                                           72  6-nitro-1-diazo-2-naphthol-                                                                  6-amino-1-naphthol-3-                                                                        grey                                            4-sulphonic acid                                                                             sulphonic acid                                             __________________________________________________________________________

EXAMPLE 73

If the metal-free azo dyestuff in Example 67 is replaced by anequivalent amount of the azo dyestuff prepared from the diazonium saltof 2-amino-4,6-dichlorophenol by coupling to8-amino-1-naphthol-3,6-disulphonic acid at pH 8, a dyestuff which dyescotton and viscose staple navy blue is obtained. In the form of the freeacid, the dyestuff corresponds to the formula ##STR32##

EXAMPLE 74

77.8 g of the dyestuff prepared from 2-amino-6-nitrophenol-4-sulphonicacid and 2-naphthol by diazotisation and coupling are stirred in 500 mlof water at 80° C.

The 1:1 chromium complex which is obtained by diazotising 44.7 g of2-amino-4-chlorophenol-6-sulphonic acid, coupling the diazotisationproduct to 72.6 g of 8-amino-1-naphthol-3,5-disulphonic acid at pH 8,chroming the coupling product with 32 g of chromium trichloride in acidsolution and salting out and filtering off the product, are introducedinto this suspension at pH 8 in the course of 1 hour.

The unsymmetric 1:2 chromium complex azo dyestuff is intermediatelyisolated and condensation reactions are carried out with 20 ml ofcyanuric fluoride at pH 5 and 0° C. and with 31 g ofN-(2-hydroxyethyl)-aniline at pH 7 and at 25° C. The dyestuff is saltedout, filtered off and dried. The dyestuff, which, in the form of thefree acid, corresponds to the formula ##STR33## dyes cotton and viscosestaple blue-grey.

EXAMPLE 75

If the 2-amino-4-chlorophenol-6-sulphonic acid in Example 74 is replacedby a corresponding amount of 2-amino-4-nitrophenol-6-sulphonic acid, anunsymmetric 1:2 chromium complex dyestuff with which cellulose materialscan be dyed or printed in blue-grey shades is obtained. Symmetric 1:2chromium complex azo dyestuffs are obtained when the diazo componentsand coupling components indicated in the following table are employedaccording to the instructions of Example 74 and condensation reactionsare carried out with cyanuric fluoride and, finally withN-(2-hydroxyethyl)-aniline.

    __________________________________________________________________________    Ex-                                                                           ample                               Colour shade                              No. Diazo component                                                                            Coupling component on cotton                                 __________________________________________________________________________    76  2-aminobenzoic acid                                                                        6-amino-1-naphthol-3-sulphonic acid                                                              brown                                     77    "          6-amino-1-naphthol-3,5-disulphonic acid                                                          brown                                     78  2-amino-4-chlorophenol                                                                     8-amino-1-naphthol-3,6-disulphonic acid                                                          blue-grey                                 79    "          8-amino-1-naphthol-3,5-disulphonic acid                                                          blue-grey                                 80  2-amino-4-nitrophenol                                                                         "               blue-grey                                 81  2-amino-5-nitrophenol                                                                         "               blue grey                                 82    "          8-amino-1-naphthol-3,6-disulphonic acid                                                          blue-grey                                 83  2-amino-4-nitrophenol                                                                         "               blue-grey                                 84  6-nitro-1-diazo-2-naphthol-                                                                6-amino-1-naphthol-3-sulphonic acid                                                              grey                                          4-sulphonic acid                                                          __________________________________________________________________________

EXAMPLE 85

If the 8-amino-1-naphthol-3,5-disulphonic acid in Example 74 is replacedby an equivalent amount of 8-amino-1-naphthol-3,6-disulphonic acid, adyestuff with which cotton and viscose staple can be dyed or printedblue-grey is obtained.

Further outstanding grey to black dyestuffs are obtained by mixingcobalt complex dyestuffs with chromium complex dyestuffs, for example bymixing Example 84 with Example 72 and Example 83 with Example 71, itbeing possible for the mixing ratio to vary between 30:70 and 70:30.

EXAMPLE 86

30.0 g of the disodium salt of1-amino-4-(4'-aminophenylamino)-anthraquinone-2,3'-disulphonic acid aredissolved in 600 ml of water. The solution is cooled to 0°-5° and the pHvalue is adjusted to 4.5. 5.6 ml of cyanuric fluoride are now addeddropwise at 0°-5° in the course of 10 minutes, the pH value is kept at4.2-4.7 with 2 N sodium carbonate solution and, after the dropwiseaddition, the mixture is subsequently stirred for 15 minutes, until theconsumption of sodium carbonate has ceased and the condensation reactionhas ended.

8.7 g of N-(2-hydroxyethyl)-aniline are now added to the solution of thedifluorotriazinyl dyestuff and the pH value of the reaction mixture iskept at 7.0-7.5. After subsequently stirring the reaction mixture forabout two hours, the temperature is 20° C. The condensation reaction hasended. The dyestuff is gradually salted out with 100 g of sodiumchloride and filtered off and the filter cake is washed with 10%strength sodium chloride solution. After drying at 40° in vacuo, adyestuff which, in the form of the free acid, corresponds to the formula##STR34## and dyes cotton, from a long liquor at 40°, in strong,greenish-tinged blue shades with very good fastness to light and wetprocessing is obtained.

EXAMPLE 87

28.0 g of1-amino-4-(5'-amino-2',4',6'-trimethylphenylamino)-anthraquinone-2,3'-disulphonicacid are dissolved, at pH 4.5, in 300 ml of water and the solution iscooled to 0°-5°. 5.2 ml of cyanuric fluoride are added dropwise in thecourse of 5 minutes and the pH value of the solution is kept at 4.5 with2 N sodium carbonate solution. The mixture is subsequently stirred atthis pH value for a further 15 minutes, 8.0 g ofN-(2-hydroxyethyl)-aniline are then added and the pH value is adjustedto 7.0-7.5 with sodium carbonate solution. Stirring is continued at thispH value for a further 1 hour, during which the temperature is allowedto rise to 20°, and the dyestuff of the formula ##STR35## is salted outwith 25 g of sodium chloride. The dyestuff is filtered off, washed with500 ml of 15% strength sodium chloride solution and dried at 40° invacuo. It dyes cotton, from a long liquor at 40°, in brillant,reddish-tinged blue shades with excellent fastness to light and wetprocessing.

EXAMPLE 88

30.0 g of 1-amino-4-(3'-aminophenylamino)-anthraquinone-2,4'-disulphonicacid are dissolved in 400 ml of water. The solution is adjusted to pH4.5 and is cooled to 0°-5°. 6.2 ml of cyanuric fluoride are addeddropwise in the course of 10-15 minutes. The acid liberated is bufferedwith 2 N sodium carbonate solution such that the pH value is keptbetween 4.2 and 4.7. After the dropwise addition, the mixture is stirredfor a further 15 minutes and 9.6 g of N-(2-hydroxyethyl)-aniline arethen added. For the condensation reaction, the pH value of the reactionsolution is kept at 6.0-6.5 with 2 N sodium carbonate solution and thetemperature is further kept at 0°-5°. After subsequently stirring themixture for one hour, the reaction has ended and the consumption ofsodium carbonate has virtually ceased. The solution is warmed to 20° andthe dyestuff is salted out with 130 g of sodium chloride in the courseof 2 hours. It is filtered off, washed with 200 ml of 20% strengthsodium chloride solution and then with 400 ml of 15% strength sodiumchloride solution and dried at 40° in vacuo. It corresponds, in the formof the free acid, to the formula ##STR36## and dyes cotton, from a longliquor, in a neutral blue shade which is fast to light and wetprocessing.

EXAMPLE 89

If 30.8 g of the disodium salt of1-amino-4-(4'-methylaminophenylamino)-anthraquinone-2,3'-disulphonicacid are employed in Example 86 instead of the anthraquinone compounddescribed in that example and the procedure is otherwise in accordancewith the instructions given in Example 86, a dyestuff which, in the formof the free acid, corresponds to the formula ##STR37## and dyes cotton,from a long liquor, in greenish-tinged blue shades which are very fastto light and wet processing is obtained.

EXAMPLE 90

36.6 g of1-amino-4-(3'-amino-2'-methyl-phenylamino)-anthraquinone-2,5'-disulphonicacid are dissolved in 150 ml of tetramethylenesulphone and 21.5 ml ofN,N-dimethylaniline. After cooling the solution to 0°-5°, 6.9 ml ofcyanuric fluoride are added dropwise in the course of 15 minutes. 10.7 gof N-(2-hydroxyethyl)aniline are dissolved in 600 ml of water. Thesolution is adjusted to a pH value of 6.0 with hydrochloric acid and iscooled to 0°-5°. The solution of the difluorotriazinylanthraquinonecomponent is then added dropwise to the aqueous hydroxyethylanilinesolution in the course of about 20 minutes and the pH value of thereaction mixture is kept at 5.5-5.7 by means of 2 N sodium carbonatesolution . After subsequently stirring the mixture for about threehours, the condensation reaction between the fluorotriazinyl componentand the hydroxyethylaniline has ended. The resulting solution is addeddropwise to 800 ml of sautrated sodium chloride solution and 240 ml ofwater and the temperature of the suspension is kept at 20°. The dyestuffof the formula ##STR38## which has precipitated is filtered off, washedwith 1 liter of 15% strength sodium chloride solution and dried at 40°in vacuo.

It dyes cotton, from a long liquor, in a neutral blue shade with goodfastness to light and wet processing.

1-Amino-4-(4'-aminophenylamino)-anthraquinone-2,2'-disulphonic acid and1-amino-4-(4'-methylaminophenylamino)-anthraquinone-2,2'-disulphonicacid can be reacted in the same manner.

EXAMPLE 91

32.0 g of the disodium salt of1-amino-4-(4'-aminophenylamino)-anthraquinone-2,2'-disulphonic acid aredissolved in 460 ml of water. The solution is adjusted to a pH value of3.5 and is cooled to 0°-5°. 5.9 ml of cyanuric fluoride are now allowedto run in over a period of 2-3 minutes and the pH value of the solutionis kept at 3.2-3.5 with 2 N sodium carbonate solution; at the same time,the temperature is kept at 0°-5° by adding a little ice. After thedropwise addition of the cyanuric fluoride, the mixture is subsequentlystirred under the conditions indicated for a further 10-15 minutes, thepH value is then adjusted to 5.5 to 9.1 g of N-(2-hydroxyethyl)-anilineare added to the solution of the difluorotriazinyl component.

The pH value is now kept at 7.0-7.5 by adding 2 N sodium carbonatesolution dropwise, and the temperature is maintained further at 0°-5°.After subsequently stirring the mixture for about three hours, thecondensation reaction has ended and the temperature has reached roomtemperature. The dyestuff, which may have partly precipitated, is saltedout with 10% strength sodium chloride solution. The dyestuff of theformula ##STR39## is dried at 40° in vacuo. It dyes cotton, from a longliquor, in greenish-tinged blue shades which are fast to light and wetprocessing.

Further anthraquinone dyestuffs are obtained in an analogous manner whenthe anthraquinone components listed in the second column of the tableare subjected to a condensation reaction with cyanuric fluoride and theintermediate products are then reacted with N-(2-hydroxyethyl)-aniline.

    ______________________________________                                        Example                      Colour shade                                     No.    Anthraquinone component                                                                             on cotton                                        ______________________________________                                        92     1-amino-4-(5'-amino-2'-methyl-                                                                      blue                                                    phenylamino)-anthraquinone-                                                   2,4'-disulphonic acid                                                  93     1-amino-4-(4'-aminophenylamino)-                                                                    greenish-                                               anthraquinone-2,4',6-trisul-                                                                        tinged blue                                             phonic acid                                                            94     1-amino-4-(5'-amino-2'-methoxy-                                                                     greenish-                                               phenylamino)-anthraquinone-2,4-                                                                     tinged blue                                             disulphonic acid                                                       95     1-amino-4-(3'-aminophenylamino)-                                                                    greenish-                                               anthraquinone-2,4',5-trisul-                                                                        tinged blue                                             phonic acid                                                            96     a mixture of 1-amino-4-(4'-amino-                                                                   greenish-                                               phenylamino)-anthraquinone-2,3',5-                                                                  tinged blue                                             and -2,3',8-trisulphonic acid                                          97     1-amino-4-(3'-aminophenylamino)-                                                                    somewhat                                                anthraquinone-2,7-disulphonic                                                                       greenish-                                               acid                  tinged blue                                      98     1-amino-4-(6'-aminomethyl-4'-                                                                       reddish-                                                methylphenylamino)-anthraquinone-                                                                   tinged blue                                             2,2'-disulphonic acid                                                  99     1-amino-4-(3'-methylaminomethyl-                                                                    reddish-                                                2',6'-dimethylphenylamino)-anthra-                                                                  tinged blue                                             quinone-2,3'- and 2,4'-disul-                                                 phonic acid                                                            100    1-amino-4-(3'-amino-4'-methyl-                                                                      blue                                                    phenylamino)-anthraquinone-2,2'-                                              disulphonic acid                                                       101    1-amino-4-(4'-methylaminomethyl-                                                                    blue                                                    phenylamino)-anthraquinone-2,2'-                                              disulphonic acid                                                       102    1-amino-4-(4'-aminophenylamino)-                                                                    greenish-                                               anthraquinone-2,6-disulphonic                                                                       tinged blue                                             acid                                                                   103    1-amino-4-(3'-aminophenylamino)-                                                                    somewhat                                                anthraquinone-2,6-disulphonic                                                                       greenish-                                               acid                  tinged blue                                      ______________________________________                                    

EXAMPLE 104

35.0 g of a dyestuff component which is formed by reacting 1 mol ofcopper phthalocyanine-3,3',3",3"'-tetrasulphonic acid chloride with 1mol of 3-aminoacetanilide, subsequently saponifying the unreactedsulphochloride groups and then saponifying the acetylamino group in hot,dilute hydrochloric acid are dissolved, at pH 6-7, in 700 ml of water.After cooling the solution to 0°-5°, the pH value is adjusted to 4.5 and3.6 ml of cyanuric fluoride are added dropwise in the course of 5minutes, during which the pH value is kept between 4.0 and 4.3 by adding20% strength sodium carbonate solution dropwise. When the reaction hasended and the consumption of sodium carbonate has ceased, 5.6 g ofN-(2-hydroxyethyl)-aniline are added and the pH value is now kept at7.0-7.5 with sodium carbonate solution. After 3 hours, the solution haswarmed to room temperature and the condensation reaction has ended. Thedyestuff, which corresponds to the formula ##STR40## is salted out withsodium chloride, filtered off and washed with sodium chloride solution.It is dried at 40° in vacuo. On cotton, from a long liquor, the dyestuffgives turquoise blue colour shades which are fast to light and wetprocessing.

Further blue or green dyestuffs are obtained when the followingphthalocyanine components are subjected to a condensation reaction withcyanuric fluoride and N-(2-hydroxy-ethyl)-aniline in an analogousmanner.

    ______________________________________                                        Example                                                                       No.    Phthalocyanine component                                                                            Color shade                                      ______________________________________                                        105    copper phthalocyanine-3,3',3"-                                                                      turquoise                                               (trisulphonic acid)-3"'-sul-                                                  phonic acid 3-amino-4-sulpho-                                                 phenylamide                                                            106    copper phthalocyanine-3,3',3"-                                                                      "                                                       (trisulphonic acid)-3"'-sul-                                                  phonic acid 4-amino-3-sulpho-                                                 phenylamide                                                            107    copper phthalocyanine-3,3',3"-                                                                      "                                                       (trisulphonic acid)-3"'-sul-                                                  phonic acid 4-amino-phenylamide                                        108    copper phthalocyanine-3,3',3"-                                                                      "                                                       (trisulphonic acid)-3"'-sul-                                                  phonic acid 2-aminoethylamide                                          109    copper phthalocyanine-3,3'-                                                                         "                                                       (disulphonic acid)-3"-sulphonic                                               acid 3-amino-4-sulpho-phenylamide                                      110    copper phthalocyanine-3,3'-                                                                         "                                                       (disulphonic acid)-3"-sulphonic                                               acid 4-amino-3-sulphophenylamide                                       111    copper phthalocyanine-3,3',3"-                                                                      "                                                       (trisulphonic acid)-3"'-sul-                                                  phonic acid 4-amino-3-carboxy-                                                phenylamide                                                            112    nickel phthalocyanine-3,3',3"-                                                                      bluish-                                                 (trisulphonic acid)-3"'-sul-                                                                        tinged green                                            phonic acid 3-aminophenylamide                                         113    nickel phthalocyanine-3,3',3"-                                                                      bluish-                                                 (trisulphonic acid)-3"'-sul-                                                                        tinged green                                            phonic acid 4-amino-3-sulpho-                                                 phenylamide                                                            114    nickel phthalocyanine-3,3',3"-                                                                      bluish                                                  (trisulphonic acid)-3"'-sul-                                                                        tinged green                                            phonic acid 4-aminophenylsulph-                                               amide                                                                  115    copper phthalocyanine-3,3',3"-                                                                      turquoise                                               (trisulphonic acid)-3"'-sul-                                                  phonic acid-4-amino-2-sulpho-                                                 phenylamide                                                            116    copper phthalocyanine-3,3',3"-                                                                      "                                                       (trisulphonic acid)-3"'-sul-                                                  phonic acid 5-amino-2-sulpho-                                                 phenylamide                                                            117    copper phthalocyanine-4,4',4"-                                                                      "                                                       (trisulphonic acid)-4"'-sul-                                                  phonic acid 3-aminophenylamide                                         118    copper phthalocyanine-4,4',4"-                                                                      "                                                       (trisulphonic acid)-4"'-sul-                                                  phonic acid 3-amino-4-sulpho-                                                 phenylamide                                                            119    copper phthalocyanine-4,4',4"-                                                                      "                                                       (trisulphonic acid)-4"'-sul-                                                  phonic acid 4-amino-3-sulpho-                                                 phenylamide                                                            120    copper phthalocyanine-3,3'-                                                                         "                                                       (disulphonic acid)-3"-(sulphonic                                              acid 3-amino-4-sulphophenylamide)-                                            3"'-sulphonic acid amide                                               121    copper phthalocyanine-3,3'-                                                                         "                                                       (disulphonic acid)-3"-(sulphonic                                              acid 4-amino-3-sulphophenylamide)-                                            3"'-sulphonic acid amide                                               ______________________________________                                    

EXAMPLE 122

The diazonium salt of 22.1 g of 2-aminophenol-4-sulphonic acid iscoupled to 19.2 g of α-formylphenylacetic acid ethyl ester at pH 8. Themixture is boiled at pH 10 for 30 minutes and the solution of thesaponification product is coupled with the diazonium salt of 23.0 g of2-amino-5-acetylaminobenzoic acid at pH 5.

Thereafter, the acetylamino group is saponified by warming the mixtureat pH 9.5 for one hour and the formazan dyestuff is salted out, isolatedand reacted with 25 g of copper-II sulphate pentahydrate at pH 3.

The dyestuff is salted out and isolated.

The dissolved paste is subjected to successive condensation reactionswith 10 ml of cyanuric fluoride at pH 5 and at 0° C. and 15.4 g ofN-(2-hydroxyethyl)-aniline at pH 7 and at 25° C. With the dyestuff ofthe formula ##STR41## cotton and viscose staple are dyed in a blue shadewhich is fast to light and washing.

EXAMPLE 128

The diazonium salt of 73.8 g of 2-amino-6-acetylaminophenol-4-sulphonicacid is coupled, at pH 9, to the hydrazone prepared from 31.8 g ofbenzaldehyde and 45.6 g of 2-hydrazinobenzoic acid. Thereafter, theacetylamino group is saponified by warming the mixture to 95° C. at pH10 for one hour. The mixture is adjusted to pH 3 with concentratedhydrochloric acid and the formazan is reacted with 75.0 g of copper-IIsulphate pentahydrate. After salting out and filtering off the dyestuff,the moist paste is stirred in 1.5 l of water and successive condensationreactions are carried out with 28 ml of cyanuric fluoride at pH 6.5 andat 0° C. and with 43.2 g of N-(2-hydroxyethyl)-aniline at pH 7 and 25°C. With the dyestuff which, in the form of the free acid, corresponds tothe formula ##STR42## cotton and viscose staple can be dyed or printedin blue shades which are fast to light and washing.

We claim:
 1. Reactive dyestuffs of the formula ##STR43## wherein Fbdenotes the radical of an organic dyestuff,W denotes a direct bond or abridge member, W being bonded to a C atom of an aromatic-carbocyclicring of the chromophor Fb, R₁ denotes hydrogen, optionally substitutedC₁ -C₄ -alkyl or aralkyl, R₂ denotes C₂ H₄ --OH, R₃ denotes hydrogen, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, carboxyl, C₁ -C₄ -alkoxycarbonyl,C₁ -C₄ -alkyl- or -dialkyl-aminocarbonyl, optionally substitutedarylaminocarbonyl, sulpho, C₁ -C₄ -alkyl- or -dialkyl-aminosulphonyl,hydroxyl, optionally substituted C₁ -C₄ -alkyl- or aryl-carbonylamino,formylamino, oxalylamino, optionally substituted ureido orsulphomethylene, n is 0, 1, 2 or 3 and m is 1 or
 2. 2. Reactivedyestuffs of the formula ##STR44## wherein Fb, W, R₁, R₂, m and n havethe meaning given in claim
 1. 3. Reactive dyestuffs of the formula##STR45## wherein Fb, W, R₁, R₂, R₃ and m have the meaning given inclaim
 1. 4. Reactive dyestuffs of claim 1, in whichm denotes 1 and Fbdenotes the radical of a water-soluble azo dyestuff, anthraquinonedyestuff, phthalocyanine dyestuff or formazan dyestuff, the radical ofsuch a dyestuff being devoid of or containing sulpho groups. 5.Dyestuffs of claim 1, in whichR₁ and R₃ denote H, R₂ denotes --CH₂ --CH₂--OH and W denotes a direct bond,the dyestuffs containing 1-8 sulphogroups.
 6. A method for dyeing and printing fibre materials, containinghydroxyl groups or nitrogen which comprises applying to said materialthe dyestuffs of claim
 1. 7. Fibre materials, containing hydroxyl groupsor nitrogen, dyed or printed with the dyestuffs of claim
 1. 8. Areactive dyestuff of claim 1 wherein R₃ is chlorine.
 9. A reactivedyestuff of claim 4 wherein the radical of said dyestuff contains sulphogroups.